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US3996259A - Oxidation of organic compounds by aqueous hypohalites using phase transfer catalysis - Google Patents

Oxidation of organic compounds by aqueous hypohalites using phase transfer catalysis Download PDF

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US3996259A
US3996259A US05/629,338 US62933875A US3996259A US 3996259 A US3996259 A US 3996259A US 62933875 A US62933875 A US 62933875A US 3996259 A US3996259 A US 3996259A
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organic compound
organic
aqueous
quaternary ammonium
hypohalite ion
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George A. Lee
Harold H. Freedman
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C07C49/665—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system
    • C07C49/675—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system having three rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

  • This invention relates to the oxidation of organic compounds by aqueous hypohalites. More particularly, this invention relates to the oxidation of organic compounds oxidizable by hypohalite ion in a biphasic mixture using phase transfer catalysis.
  • Oxidations catalyzed by quaternary onium salts have been reported by C. M. Starks, J. Amer. Chem. Soc., 93, 195 (1971). There, nonanoic acid was prepared in 91 percent yield by reacting aqueous potassium permanganate with 1-decene in the presence of tricaprylmethylammonium chloride. However, no such catalyzed reaction has been reported where hypohalite ion was the oxidizing agent.
  • a novel process for oxidizing organic compounds oxidizable by hypohalite ion in a biphasic mixture using phase transfer catalysis comprises reacting by contacting:
  • the novel process proceeds under mild conditions in high yields and in reduced reaction time.
  • the phase transfer catalyzed hypohalite oxidations are more efficient than the noncatalyzed hypohalite oxidations.
  • said catalyzed hypohalite oxidations are highly selective.
  • a secondary alcohol is quantitatively oxidized by this invention to a ketone before the ketone itself is oxidized via the haloform reaction to a carboxylic acid.
  • Any organic compound oxidizable by aqueous hypohalite ion can be oxidized by this invention.
  • Illustrative of these compounds are amines, amides, alkanals, primary and secondary alkanols, and organic compounds containing an activated double bond, i.e. an organic compound containing the structure ##STR1## wherein Z is an electron withdrawing group, such as carbonyl, nitrile, ester, etc.
  • Typical oxidation reactions include amines to N-haloimines or nitriles, amides to N-haloimines or nitriles, alkanals to carboxylic acids, primary alkanols to alkanals, secondary alkanols to ketones, and enones to epoxies, i.e., 2-cyclohexenone to 2-cyclohexenone oxide.
  • hypohalites here used are hypochlorite, hypobromite, hypoiodite, or any combination thereof. Any suitable source of hypohalite ion can be used in the practice of this invention, but typically the alkali metal hypohalites are used. Due to reasons of familiarity and general availability, hypochlorite is preferred over the other hypohalites.
  • the catalysts here used are quaternary ammonium and phosphonium salts and are known in the art as phase transfer catalysts.
  • the salts are described by Starks and Napier in British patent 1,227,144 and by Starks in the J. Amer. Chem. Soc., 93, 195 (1971).
  • Suitable onium salts have a minimum solubility of at least about 1 weight percent in both the organic phase and the aqueous phase at 25° C.
  • the ammonium salts are preferred over the phosphonium salts and benzyltrimethyl-, benzyltriethyl-, and tetra-n-butylammonium chlorides and bromides are most preferred.
  • suitable ammonium salts are represented by the formula R 1 R 2 R 3 R 4 N +A - wherein R 1 -R 4 are hydrocarbyl groups, i.e. alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl, etc., and R 1 can join with R 2 , or R 2 with R 3 , etc. to form a 5- or 6-membered heterocyclic compound having at least 1 quaternized nitrogen atom in the ring and may also contain 1 non-adjacent atom of oxygen or sulfur within the ring.
  • R 1 -R 4 are hydrocarbyl groups of from 1 to about 16 carbon atoms each, with a combined minimum total of about 10 carbon atoms.
  • Preferred ammonium salts have from about 10 to about 30 carbon atoms.
  • a similar formula can be drawn for the phosphonium salts.
  • the neutralizing anion portion of the salt i.e. A - in the above generic formula, may be varied to convenience.
  • Chloride and bromide are the preferred anions, but other representative anions include fluoride, iodide, tosylate, acetate, bisulfate, etc.
  • tetraalkylammonium salts such as tetra-n-butyl-, tri-n-butylmethyl-, tetrahexyl-, trioctylmethyl-, hexadecyltriethyl-, and tridecylmethyl-ammonium chlorides, bromides, iodides, bisulfates, tosylates, etc; aralkylammonium salts, such as tetrabenzyl-, benzyltrimethyl-, benzyltriethyl-, benzyltributyl-, and phenethyltrimethylammonium chlorides, bromides, iodides, etc; arylammonium salts, such as triphenylmethylammonium fluoride, chloride or bromide, N,N,N-trimethylanilinium chloride, N,N,N-triethylanilinium bromid
  • hypohalite ion preferably an excess of hypohalite ion is employed to promote a quantitative reaction.
  • the particular ratio of organic compound to hypohalite ion will vary with the particular reagents. For example, amines are oxidized in best yields when at least a 2-fold excess of hypohalite ion is used. For amide oxidization, at least a 4-fold excess of hypohalite ion is desirable. The determination of the proper ratio of reagents is well within the skill of the ordinary artisan.
  • a catalytic amount of the onium salt is required in the practice of this invention. Again, the concentration will vary with particular reagents employed. However, best results are generally achieved when the onium salt concentration is from about 1 mole percent to about 30 mole percent based upon the organic compound to be oxidized. Concentrations between about 2 mole percent and about 10 mole percent are preferred.
  • reaction can be conducted neat, it is preferably conducted in the presence of an inert, water-immiscible organic solvent.
  • Typical solvents include benzene, chlorobenzene, o-dichlorobenzene, hexane, methylene chloride, chloroform, carbon tetrachloride, and the like. Not only do these solvents contribute to the formation of a biphasic reaction mixture, but they also aid in moderating reaction rate and temperature.
  • the amount of solvent used is equal in volume to the amount of aqueous hypohalite used. Practical considerations of reaction vessel size, product recovery, etc. are the only limitations upon the maximum amount of solvent that can be used.
  • p-Methylbenzyl alcohol (1.2515 g, 0.0103 mole) 2-chloronaphthalene (0.8747 g, used as an internal standard for gas chromatography), and tetra-n-butylammonium bisulfate (0.1841 g, 0.0005 mole) were dissolved in 25 ml of methylene chloride. To this solution was added 25 ml of 12 percent aqueous sodium hypochlorite (2.95 g, 0.04 mole). The biphasic mixture was stirred under ambient conditions (24° C, atmospheric pressure) and monitored periodically by gas chromatography. After 1.9 hours reaction time, 85.2 percent of the p-methylbenzyl alcohol had been converted to p-tolualdehyde.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Organic compounds oxidizable by hypohalite ion, such as amines, amides, primary and secondary alcohols, and alkanals are efficiently oxidized in a biphasic mixture comprising:
A. a water immiscible, liquid organic phase comprising an organic compound oxidizable by hypohalite ion; with
B. an aqueous phase containing hypohalite ion; and
C. a catalytic amount of a quaternary ammonium salt and/or a quaternary phosphonium salt.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the oxidation of organic compounds by aqueous hypohalites. More particularly, this invention relates to the oxidation of organic compounds oxidizable by hypohalite ion in a biphasic mixture using phase transfer catalysis.
2. Description of the Prior Art
Various methods are known for oxidizing organic compounds by hypohalite ion. For example, C. Y. Meyers, J. Org. Chem., 26, 1046 (1961), teaches the preparation of benzaldehyde by reacting benzyl alcohol with aqueous, methanolic inorganic hypochlorite. E. S. Wallis and J. F. Lane, Org. Reactions, 3, 267 (1947), teach the Hoffman rearrangement of amides to amines by reacting alkali metal hypohalite and a primary amide in aqueous caustic.
Oxidations catalyzed by quaternary onium salts have been reported by C. M. Starks, J. Amer. Chem. Soc., 93, 195 (1971). There, nonanoic acid was prepared in 91 percent yield by reacting aqueous potassium permanganate with 1-decene in the presence of tricaprylmethylammonium chloride. However, no such catalyzed reaction has been reported where hypohalite ion was the oxidizing agent.
SUMMARY OF THE INVENTION
A novel process for oxidizing organic compounds oxidizable by hypohalite ion in a biphasic mixture using phase transfer catalysis has been discovered. The process comprises reacting by contacting:
A. A WATER-IMMISCIBLE, LIQUID ORGANIC PHASE COMPRISING AN ORGANIC COMPOUND OXIDIZABLE BY HYPOHALITE ION; WITH
B. AN AQUEOUS PHASE CONTAINING HYPOHALITE ION; AND
C. A CATALYTIC AMOUNT OF A QUATERNARY AMMONIUM SALT AND/OR A QUATERNARY PHOSPHONIUM SALT. The novel process proceeds under mild conditions in high yields and in reduced reaction time. In every case, the phase transfer catalyzed hypohalite oxidations are more efficient than the noncatalyzed hypohalite oxidations. Moreover, said catalyzed hypohalite oxidations are highly selective. For example, a secondary alcohol is quantitatively oxidized by this invention to a ketone before the ketone itself is oxidized via the haloform reaction to a carboxylic acid.
DETAILED DESCRIPTION OF THE INVENTION
Any organic compound oxidizable by aqueous hypohalite ion can be oxidized by this invention. Illustrative of these compounds are amines, amides, alkanals, primary and secondary alkanols, and organic compounds containing an activated double bond, i.e. an organic compound containing the structure ##STR1## wherein Z is an electron withdrawing group, such as carbonyl, nitrile, ester, etc. Typical oxidation reactions include amines to N-haloimines or nitriles, amides to N-haloimines or nitriles, alkanals to carboxylic acids, primary alkanols to alkanals, secondary alkanols to ketones, and enones to epoxies, i.e., 2-cyclohexenone to 2-cyclohexenone oxide.
The hypohalites here used are hypochlorite, hypobromite, hypoiodite, or any combination thereof. Any suitable source of hypohalite ion can be used in the practice of this invention, but typically the alkali metal hypohalites are used. Due to reasons of familiarity and general availability, hypochlorite is preferred over the other hypohalites.
The catalysts here used are quaternary ammonium and phosphonium salts and are known in the art as phase transfer catalysts. The salts are described by Starks and Napier in British patent 1,227,144 and by Starks in the J. Amer. Chem. Soc., 93, 195 (1971). Suitable onium salts have a minimum solubility of at least about 1 weight percent in both the organic phase and the aqueous phase at 25° C. The ammonium salts are preferred over the phosphonium salts and benzyltrimethyl-, benzyltriethyl-, and tetra-n-butylammonium chlorides and bromides are most preferred.
To further illustrate the type of ammonium salt which can be used, suitable ammonium salts are represented by the formula R1 R2 R3 R4 N+A - wherein R1 -R4 are hydrocarbyl groups, i.e. alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl, etc., and R1 can join with R2, or R2 with R3, etc. to form a 5- or 6-membered heterocyclic compound having at least 1 quaternized nitrogen atom in the ring and may also contain 1 non-adjacent atom of oxygen or sulfur within the ring. Typically, R1 -R4 are hydrocarbyl groups of from 1 to about 16 carbon atoms each, with a combined minimum total of about 10 carbon atoms. Preferred ammonium salts have from about 10 to about 30 carbon atoms. A similar formula can be drawn for the phosphonium salts.
The neutralizing anion portion of the salt, i.e. A- in the above generic formula, may be varied to convenience. Chloride and bromide are the preferred anions, but other representative anions include fluoride, iodide, tosylate, acetate, bisulfate, etc. The following compounds serve as a further illustration: tetraalkylammonium salts, such as tetra-n-butyl-, tri-n-butylmethyl-, tetrahexyl-, trioctylmethyl-, hexadecyltriethyl-, and tridecylmethyl-ammonium chlorides, bromides, iodides, bisulfates, tosylates, etc; aralkylammonium salts, such as tetrabenzyl-, benzyltrimethyl-, benzyltriethyl-, benzyltributyl-, and phenethyltrimethylammonium chlorides, bromides, iodides, etc; arylammonium salts, such as triphenylmethylammonium fluoride, chloride or bromide, N,N,N-trimethylanilinium chloride, N,N,N-triethylanilinium bromide, N,N-diethylanilinium bisulfate, trimethylnaphthyl ammonium chloride, p-methylphenyltrimethylammonium chloride or tosylate, etc; 5- and 6-membered heterocyclic compounds containing at least 1 quaternary nitrogen atom in the ring, such as N,N-dibutylmorpholinium chloride, N-decylthiazolium chloride, etc, and the corresponding phosphonium salts.
Although stoichiometric amounts of oxidizable organic compound and hypohalite ion are necessary, preferably an excess of hypohalite ion is employed to promote a quantitative reaction. Of course, the particular ratio of organic compound to hypohalite ion will vary with the particular reagents. For example, amines are oxidized in best yields when at least a 2-fold excess of hypohalite ion is used. For amide oxidization, at least a 4-fold excess of hypohalite ion is desirable. The determination of the proper ratio of reagents is well within the skill of the ordinary artisan.
A catalytic amount of the onium salt is required in the practice of this invention. Again, the concentration will vary with particular reagents employed. However, best results are generally achieved when the onium salt concentration is from about 1 mole percent to about 30 mole percent based upon the organic compound to be oxidized. Concentrations between about 2 mole percent and about 10 mole percent are preferred.
Temperature and pressure are not critical to this invention as long as the biphasic mixture remains a liquid. Best results are obtained when the reaction temperatures range from about 0° to about 35° C with ambient temperature and pressure preferred.
Although the reaction can be conducted neat, it is preferably conducted in the presence of an inert, water-immiscible organic solvent. Typical solvents include benzene, chlorobenzene, o-dichlorobenzene, hexane, methylene chloride, chloroform, carbon tetrachloride, and the like. Not only do these solvents contribute to the formation of a biphasic reaction mixture, but they also aid in moderating reaction rate and temperature.
Generally, at least sufficient solvent to dissolve the oxidizable organic compound is used and preferably the amount of solvent used is equal in volume to the amount of aqueous hypohalite used. Practical considerations of reaction vessel size, product recovery, etc. are the only limitations upon the maximum amount of solvent that can be used.
The following examples are illustrative embodiments of this invention.
EXAMPLE 1
A solution of benzyl alcohol (1 g, 0.0093 mole), naphthalene (1.02 g, used as an internal standard for gas chromatography), and tetra-n-butylammonium chloride (0.122 g, 0.00044 mole) in 40 ml of methylene chloride, was stirred at approximately 23° C with 40 ml of 12 percent aqueous sodium hypochlorite solution (4.96 g, 0.067 mole). The reaction mixture was occasionally cooled by an external water bath to keep the reaction temperature from exceeding 30° C. The reaction was monitored by gas chromatography. At 6.8 hours reaction time, 97 percent of the benzyl alcohol had been converted to benzaldehyde.
EXAMPLE 2
p-Methylbenzyl alcohol (1.2515 g, 0.0103 mole) 2-chloronaphthalene (0.8747 g, used as an internal standard for gas chromatography), and tetra-n-butylammonium bisulfate (0.1841 g, 0.0005 mole) were dissolved in 25 ml of methylene chloride. To this solution was added 25 ml of 12 percent aqueous sodium hypochlorite (2.95 g, 0.04 mole). The biphasic mixture was stirred under ambient conditions (24° C, atmospheric pressure) and monitored periodically by gas chromatography. After 1.9 hours reaction time, 85.2 percent of the p-methylbenzyl alcohol had been converted to p-tolualdehyde.
EXAMPLE 3
A mixture of α-phenylacetamide (1.3535 g, 0.01 mole), nitrobenzene (1.034 g, employed as an internal standard for gas phase chromatography) and tetra-n-butylammonium bisulfate (0.125 g, 0.00037 mole) in 25 ml of methylene chloride was stirred under ambient conditions (23° C, atmospheric pressure) with 50 ml of 12 percent aqueous sodium hypochlorite (5.85 g, 0.079 mole). After 2.5 hours reaction time, the organic phase was analyzed by vapor phase chromatography and was found to contain 62 percent benzonitrile.
EXAMPLES 4-11
Under conditions similar to Example 1, various other organic compounds were oxidized. The particular reagents and results are tabulated in Table I.
                                  TABLE I                                 
__________________________________________________________________________
  Organic   Quaternary                                                    
                   Alkali Metal                                           
  Compound  Onium Salt                                                    
                   Hypohalite   Reaction                                  
                                      Product                             
Ex                                                                        
  (Mole)    (Mole) (Mole)  Solvent                                        
                                (minutes)                                 
                                      (%)                                 
__________________________________________________________________________
4 p-Nitrobenzyl                                                           
            Bu.sub.4 NCl.sup.1                                            
                   KOCl    CH.sub.2 Cl.sub.2                              
                                 65   p-Nitrobenzaldehyde                 
  Alcohol (0.086)                                                         
            (0.008)                                                       
                   (0.04)             (83)                                
5 o-Methoxybenzyl                                                         
            Bu.sub.4 NHSO.sub.4.sup.2                                     
                   NaOCl   CH.sub.2 Cl.sub.2                              
                                316   o-Methoxybenzalde-                  
  Alcohol (0.4)                                                           
            (0.02) (0.04)             hyde (84)                           
6 p-Chlorobenzyl                                                          
            Bu.sub.4 NHSO.sub.4                                           
                   NaOCl   CH.sub.2 Cl.sub.2                              
                                335   p-Chlorobenzalde-                   
  Alcohol (0.4)                                                           
            (0.02) (0.04)             hyde (98)                           
7 9-Fluorenol                                                             
            Bu.sub.4 NHSO.sub.4                                           
                   NaOCl   CH.sub.2 Cl.sub.2                              
                                 51   9-Fluorenone                        
  (0.4)     (0.02) (0.04)             (93)                                
8 Benzhydrol                                                              
            Bu.sub.4 NHSO.sub.4                                           
                   NaOCl   CH.sub.2 Cl.sub.2                              
                                345   Benzophenone                        
  (0.4)     (0.02) (0.04)             (95)                                
9 Norbornyl ammonium                                                      
            Bu.sub.4 NCl                                                  
                   NaOCl   CHCl.sub.3                                     
                                 90   Norbornanone                        
  chloride (0.01)                                                         
            (0.0002)                                                      
                   (0.08)             (70)                                
10                                                                        
  Cyclohexylamine                                                         
            Bu.sub.4 NCl                                                  
                   NaOCl   CH.sub.2 Cl.sub.2                              
                                120   Cyclohexanone (38)                  
  (0.01)    (0.0002)                                                      
                   (0.08)             2-chlorocyclo-                      
                                      hexanone (55)                       
11                                                                        
  n-Octyl Amine                                                           
            Bu.sub.4 NCl                                                  
                   NaOCl   CH.sub.2 Cl.sub.2                              
                                 95   Octanoyl Nitrile                    
  (0.01)    (0.0005)                                                      
                   (0.08)             (57)                                
__________________________________________________________________________
 Footnotes:                                                               
 .sup.1 Tetra-n-butylammonium chloride                                    
 .sup.2 Tetra-n-butylammonium bisulfate

Claims (13)

What is claimed is:
1. A process for oxidizing an organic compound selected from the group consisting of amines, amides, alkanals, primary and secondary alkanols, and organic compounds containing an activated double bond with aqueous hypohalite ion comprising reacting by contacting:
a. a water-immiscible, liquid organic phase comprising the organic compound; with
b. an aqueous phase containing hypohalite ion; and
c. a catalytic amount of a quaternary ammonium salt and/or a quaternary phosphonium salt.
2. The process of claim 1 wherein the hypohalite ion is hypochlorite.
3. The process of claim 2 wherein the quaternary ammonium and phosphonium salts are of the formula R1 R2 R3 R4 Q+A - wherein Q+ is a quaternized nitrogen or phosphorus atom, A- is a neutralizing anion, and R1 -R4 are individually hydrocarbyl groups of from 1 to about 16 carbon atoms each, with a combined minimum total of about 10 carbon atoms.
4. The process of claim 3 wherein the quaternary ammonium and phosphonium salts have from about 10 to about 30 carbon atoms.
5. The process of claim 2 wherein the quaternary ammonium salt is tetra-n-butylammonium-, benzyltriethylammonium-, or benzyltrimethylammonium chloride or bisulfate.
6. The process of claim 5 wherein the reaction is conducted at a temperature of from about 0° to about 35° C.
7. The process of claim 6 wherein the water-immiscible, liquid organic phase comprises the organic compound and an inert, water-immiscible organic solvent.
8. The process of claim 1 wherein the organic compound is a primary or secondary alkanol.
9. The process of claim 1 wherein the organic compound is 9-fluorenol, benzhydrol, or benzyl, p-methylbenzyl, p-nitrobenzyl, o-methoxybenzyl or p-chlorobenzyl alcohol.
10. The process of claim 1 wherein the organic compound is an amine or amide.
11. The process of claim 1 wherein the organic compound is α-phenylacetamide, cyclohexylamine, n-octyl amine or norbornyl ammonium chloride.
12. The process of claim 1 wherein the organic compound is an alkanal.
13. The process of claim 1 wherein the organic compound contains an activated double bond.
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US4079075A (en) * 1975-11-06 1978-03-14 The Dow Chemical Company Primary alkyl esters as mediums for oxidations by phase-transfer catalyzed hypohalites
US4146582A (en) * 1976-01-30 1979-03-27 Brichima S.P.A. Process for preparing aromatic aldehydes and ketones
FR2415614A1 (en) * 1978-01-27 1979-08-24 Sigma Tau Ind Farmaceuti PROCESS FOR THE PREPARATION OF ALDEHYDES AND AROMATIC ALCOHOLS, IN PARTICULAR OF BENZALDEHYDE, BENZYL ALCOHOL AND THEIR DERIVATIVES
US4185018A (en) * 1978-08-21 1980-01-22 Ciba-Geigy Corporation Process for producing benzofurazan-1-oxides
US4198351A (en) * 1977-04-15 1980-04-15 Celanese Corporation Formaldehyde production process
US4225506A (en) * 1978-05-30 1980-09-30 Hoffmann-La Roche Inc. Process for manufacturing a diketone
EP0028488A1 (en) * 1979-10-25 1981-05-13 Unilever Plc Process for bleaching naturally occurring oils and fats
JPS5671057A (en) * 1979-10-26 1981-06-13 Ugine Kuhlmann Manufacture of 33cyanoo3*5*55trimethyll cyclohexanone
US4284573A (en) * 1979-10-01 1981-08-18 The Dow Chemical Company Preparation of glycidyl ethers
US4328170A (en) * 1978-11-02 1982-05-04 Matsumoto Seiyaku Kogyo Kabushiki Kaisha Process for preparing an α-cyanoacrylate
JPS57183773A (en) * 1981-05-06 1982-11-12 Asahi Chem Ind Co Ltd Preparation of hexafluoropropylene oxide
JPS5978176A (en) * 1982-10-27 1984-05-04 Asahi Chem Ind Co Ltd Preparation of hexafluoropropylene oxide
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Cited By (27)

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US4079075A (en) * 1975-11-06 1978-03-14 The Dow Chemical Company Primary alkyl esters as mediums for oxidations by phase-transfer catalyzed hypohalites
US4146582A (en) * 1976-01-30 1979-03-27 Brichima S.P.A. Process for preparing aromatic aldehydes and ketones
US4198351A (en) * 1977-04-15 1980-04-15 Celanese Corporation Formaldehyde production process
FR2415614A1 (en) * 1978-01-27 1979-08-24 Sigma Tau Ind Farmaceuti PROCESS FOR THE PREPARATION OF ALDEHYDES AND AROMATIC ALCOHOLS, IN PARTICULAR OF BENZALDEHYDE, BENZYL ALCOHOL AND THEIR DERIVATIVES
US4225506A (en) * 1978-05-30 1980-09-30 Hoffmann-La Roche Inc. Process for manufacturing a diketone
US4185018A (en) * 1978-08-21 1980-01-22 Ciba-Geigy Corporation Process for producing benzofurazan-1-oxides
US4328170A (en) * 1978-11-02 1982-05-04 Matsumoto Seiyaku Kogyo Kabushiki Kaisha Process for preparing an α-cyanoacrylate
US4284573A (en) * 1979-10-01 1981-08-18 The Dow Chemical Company Preparation of glycidyl ethers
EP0028488A1 (en) * 1979-10-25 1981-05-13 Unilever Plc Process for bleaching naturally occurring oils and fats
US4325883A (en) * 1979-10-25 1982-04-20 Lever Brothers Company Process for bleaching naturally-occurring oils and fats
JPS5671057A (en) * 1979-10-26 1981-06-13 Ugine Kuhlmann Manufacture of 33cyanoo3*5*55trimethyll cyclohexanone
US4299775A (en) * 1979-10-26 1981-11-10 Pcuk Produits Chimiques Ugine Kuhlmann Process for the preparation of 3-cyano-3,5,5-trimethylcyclohexanone
JPS57183773A (en) * 1981-05-06 1982-11-12 Asahi Chem Ind Co Ltd Preparation of hexafluoropropylene oxide
US4902810A (en) * 1981-05-06 1990-02-20 Asahi Kogaku Kogyo Kabushiki Kaisha Process for the production of hexafluoropropylene oxide
US4925961A (en) * 1981-05-06 1990-05-15 Asahi Kasei Kogyo Kabushiki Kaisha Process for the production of hexafluoropropylene oxide
US5055601A (en) * 1982-07-26 1991-10-08 Asahi Kasei Kogyo K.K. Fluoroepoxides and a process for production thereof
US4965379A (en) * 1982-07-26 1990-10-23 Asahi Kasei Kogyo Kabushiki Kaisha Fluoroepoxides and a process for production thereof
JPS5978176A (en) * 1982-10-27 1984-05-04 Asahi Chem Ind Co Ltd Preparation of hexafluoropropylene oxide
US4524214A (en) * 1983-11-03 1985-06-18 Stauffer Chemical Company Process for forming esters of glyoxylic acids
EP0340703A1 (en) * 1988-05-06 1989-11-08 BASF Aktiengesellschaft Process for the production of formyl cyclopropane
US5053550A (en) * 1988-05-06 1991-10-01 Basf Aktiengesellschaft Preparation of formylcyclopropane
WO1991011419A1 (en) * 1990-01-31 1991-08-08 Olin Corporation Hypochlorous acid as a reagent for the oxidation of organic compounds in two phase systems
US5068408A (en) * 1990-01-31 1991-11-26 Olin Corporation Hypochlorous acid as a reagent for the oxidation of organic compounds in two phase systems
US5227501A (en) * 1991-05-14 1993-07-13 Shin-Etsu Chemical Co., Ltd. Iodine- and fluorine-containing epoxy compound
WO1993014054A1 (en) * 1992-01-21 1993-07-22 Hoechst Schering Agrevo Gmbh Process for producing trifluoromethyl ketones
US5608062A (en) * 1992-01-21 1997-03-04 Hoechst Schering Agrevo Gmbh Process for preparing trifluoromethyl ketones
JP3282338B2 (en) 1993-12-28 2002-05-13 宇部興産株式会社 Manufacturing method of Heliotropin

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